{60 -Aryl-b-(amino-phenyl)acrylonitriles with an O-dialkyl sulphamidoxy or sulfuric acid semi-ester group

ABSTRACT

Beta -Phenyl-acrylic acid nitriles of the general formula   IN WHICH X stands for a substituent; n denotes the numbers 0 to 3; R1 stands for an optionally substituted phenyl or naphthyl group, for an aromatic-heterocyclic radical which is linked via a carbon atom to the Alpha -carbon atom of the Beta -phenylacrylonitrile radical, or for a carboxyl group; and R stands for an alkyl group, for a radical   WHERE R2 and R3 denote an alkyl radical, for a radical -So3Z where Z denotes H or a metal atom, or for a radical -CH2OR4 where R4 denotes an alkyl, aralkyl or aryl radical, and a process for their production characterised by treating toluene derivatives of the formula   WHEREIN X, n and R have the meanings given above in an aqueousalkaline medium at temperatures of about 50* to 120*C with an alkali metal polysulphide and subsequently without intermediate isolation with nitriles of the formula

United States Patent Knupfer et a].

[ June 17, 1975 a-ARYL-B-(AMINO- PHENYL)ACRYLONITRILES WITH AN O-DIALKYL SULPHAMIDOXY OR SULFURIC ACID SEMI-ESTER GROUP [75] Inventors: Hans Knupfer, Berg, Neukirchen;

Carl-Wolfgang Schellhammer, Opladen, both of Germany Bayer Aktiengesellschaft, Leverkusen-Bayerwerk, Germany [22 Filed: Dec. 11, 1972 [211 App]. No.: 313,676

Related US. Application Data [63] Continuation of Ser. No. 849,867, Aug. 13, 1969,

abandonedv [73] Assignee:

[30] Foreign Application Priority Data Aug. 23, 1968 Germany 1793261 [52] US. Cl... 260/456 A; 260/240 D; 260/343.2 R;

260/465 D; 260/465 E [51] Int. Cl C07c 121/00; C07c 137/00 [58] Field of Search 260/465 E, 465 D, 465 A [56] References Cited UNITED STATES PATENTS 3,514,471 5/1970 Yanagisawa ct al. 260/465 X Primary ExaminerLewis Gotts Assistant Examiner-Dolph H. Torrence Attorney, Agent, or Firm-Plumley & Tyner [57] ABSTRACT B-Phenyl-acrylic acid nitriles of the general formula ON on, 1

x CHzC 1 JJ H N 0R in which X stands for a substituent; n denotes the numbers 0 to 3; R stands for an optionally substituted phenyl or naphthyl group, for an aromaticheterocyclic radical which is linked via a carbon atom to the a-carbon atom of the B-phenyl-acrylonitrile radical, or for a carboxyl group; and R stands for an alkyl group, for a radical where R and R denote an alkyl radical, for a radical S Z where Z denotes H or a metal atom, or for a radical Cl-I2OR4 where R4 denotes an alkyl, aralkyl or aryl radical, and a process for their production characterised by treating toluene derivatives of the formula wherein X, n and R have the meanings given above in an aqueousalkaline medium at temperatures of about 50 to 120C with an alkali metal polysulphide and subsequently without intermediate isolation with nitriles of the formula 4 Claims, No Drawings 1 a-ARYL-B-(AMINO-PHENYL)ACRYLONITRILES WITH AN O-DIALKYL SULPHAMIDOXY OR SULFURIC ACID SEMI-ESTER GROUP This is a Continuation, of application, Ser. No. 5

849,867 filed Aug. l3, 1969 now abandoned.

The subject-mattter of the present invention comprises B-phenyl-acrylic acid nitriles of the general formula CN (io (I) H N OR in which X stands for a substituent, preferably an alkyl group with l to 4 carbon atoms; n denotes the numbers 0 to 3; R, denotes an optionally substituted phenyl or naphthyl group, an aromatic-heterocyclic radical which is linked to the a-carbon atom of the B-phenylacrylonitrile radical via a carbon atom, or denotes a carboxyl group; and R stands for an alkyl group, preferably with 1 to 4 carbon atoms, for a radical 20 aryl radicals or heterocyclic radicals;

Compounds of the formula (I) R x .11 Q

H '0 -c' H H I' H @C l -ca H L {I on -CH5(6) G H co H 5 H -co n v-c u H G61 -SO2N(CH3)2 H G -sO N(GH H @05 -sc 1 1(ca H @003 -so Mon H 2? 3 ..s0 rt(cn H Q c1 so n(cu H 61 c1 SO2N(CH3)2 a 6 The process according to the invention consists in that toluene derivatives of the general formula in which X, n and R have the same meaning as above, are first treated in an aqueous-alkaline medium, preferably in the presence of organic solvents,'at temperatures of about 50 to 120C with an alkali metal polysulphide, and the product is subsequently reacted, without intermediate isolation, preferably at temperatures of to 120C, with nitriles of the formula R5 CH2 um ple, an alcohol or dimethyl sulphoxide, at temperatures of about 50 to C with at least the amount of an aqueous-alkaline polysulphide solution required for reduction of the nitro group or oxidation of the methyl group, heating at 50 to 120C for about /2 to 3 hours, subsequently adding, possibly after cooling, about 0.7 to 1 mol of the nitrile (Ill), heating for a prolonged time, if desired, and subsequently isolating the reaction product in the usual way.

Suitable toluene derivatives of the formula (II), are, for example; 2-methoxy-4-nitro-toluene, 2-ethoxy-4- nitro-toluene, 2-n-butoxy-4-nitro-toluene, Z-methoxy- 4-nitro-6-methyl-toluene, N,N-dimethylsulfamic acid- (Z-methyI-S-nitro-phenyl) ester, (2-N,N- dimethylsulfamidoxy-4-nitro-toluene), N,N-dimethylsulfamic acid-(2,4-dimethyl-S-nitro-phenyl) ester, Na-

or K-salt of the sulphuric acid(2-methyl-5-nitro-' phenyl)-semi esters, 2-(methoxymethoxy)-4-nitrotoluene.

Suitable nitrilesofthe general formula (III) are, for example: phenyl-acetonitrile, p-tolyl-acetonitrile, mtolyl-acetonitrile, -(3,S-dimethyl-phenyl)-acetonitrile, (4-chloro-phenyl)-acetonitrile, (3,4-dichlorophenyl)- adetonitrile, (4-methyl-sulphonyl-phenyl)-acetonitrile,

(4-methoxy-phcnyl )-a'cetonitrile, naphthyll acetonitrile, naphthyl-2 acetonitrile thienyl-2- acetonitrile, pyridine-Q-acetonitrile. pyridine-3- The term alkyl-polysulphidcs refers to polysulphides which can be obtained by dissolving sulphurin an aqueous alkali metal hydroxide and/or alkali metal sulphide; the preferred alkali metal compounds are the sodium or potassium compounds.

It was known from .1. Chem. Soc. 1927, page 1741, to prepare 2-a1koxy-4-acylamino-benzaldehydes from 2-alkoxy-4-nitro-toluenes by reduction with an alkaline polysulphide solution and subsequent acylation. It was also known from Swiss Patent Specification No. 341,834 to react 2-alkoxy-4-acylamino-benzaldehydes with substituted acetonitriles to form B-(acylaminoalkoxyphenyl)-acrylic acid nitriles. It is there stated that the presence of a free aminogroup in the alkoxybenzaldehyde gives rise to interfering side reactions. In view of the aforesaid state of the art it was new and completely surprising that the two reactions, i.e. the aldehyde formation and the condensation to form the B-phenyl-acrylic acid nitrile can be carried out in a single-pot reaction, even if starting compounds are used which intermediarily yield 4-amino-2-alkoxybenzaldehydes, and that B-phenyl-acrylic acid nitriles can be obtained by the process according to the invention in a high yield, with a high degree of purity and in a simple way while avoiding an acylation reaction.

The compounds of the formula (1) are valuable intermediates for the production of optical brightening agents, as they can easily be converted into the corresponding coumarins of the formula by reaction with acids, for. example, by heating with at least 2 mol of a mineral acid at about 80 200C.

C oumarins of this type and the use thereof as brightening agents and for the production of brightening agents are known, for example, from US. Pat. Nos. 2,884,286; 2,929,822; 2,945,033; 2,242,177; and Belgian Pat. Specification No. 660,602.

The parts given in the Examples are parts by weight, the temperatures refer to degrees Centigrade.

EXAMPLE 1 A solution of 24 parts Na S 9 H 0, 19 parts sodium hydroxide and parts sulphur in 100 parts of water is added dropwise to a boiling solution of 46 parts 2-methoxy-4-nitro-toluene in 160 parts ethanol and 100 parts of water. The mixture is boiled for 1 /2 hours, 28 parts benzyl cyanide are added, boiling is continued for one hour, and the product is filtered off with suction when the mixture has cooled to 20. Parts a-phenyl- B-(2-methoxy-4-aminophenyl) -acry1onitrile of m.p. 140 to 141 are obtained,

If the 28 parts benzyl cyanide are replaced with 30 parts 4-ehloro-benzyl cyanide, then 36 parts a-(4- chlorophenyl )-B-( 2-methoxy-4-aminophenyl aerylonitrile of m.p. 228 to 229 are obtained; the use of 18 parts thienyl-2-acetonitrile leads to 26 parts a-(thienyl-2 )-fi-( 2-methoxy-4-aminophenyl) -acrylonitrile of m.p. 168 to 169.

EXAMPLE 2 A solution of 24 parts Na s 9 H 0, 19 parts NaOH and 10 parts sulphur in parts of water isadded dropwise at boiling temperature to a solution of 54.5 parts (2-methyl-5-nitro-phenoxy)-dimethyl ether (prepared from 2-hydroxy-4-nitro-toluene and chlorodimethyl ether) in 158 parts ethanol and 100 parts of water. The mixture is boiled for 1 /2 hours, 28 parts benzyl cyanide are added, boiling is continued for 60 minutes, and the mixture is allowed to cool to 20. After filtering off with suction and washing with 50% ethanol, there are obtained 21 parts a-phenyl-B-[2- (methoxy-methoxy)-4-amino-phenyl]-acrylonitrile of m.p. 855 to 86. 1

EXAMPLE 3 'A solution of 13.2 parts Na s 3 HO, 19 parts NaOH and 10 parts sulphur in 100 parts of water is added dropwise within 10 to 20 minutes to a boiling solution of 72 parts N,N-dimethyl-sulphamic acid-(Z-methyl-S- nitro-phenyl) ester (prepared from 2-hydroxy-4-nitrotoluene and N,N-dimethy1-sulphamic acid chloride) in 158 parts ethanol and 100 parts of water. The mixture is boiled for 1 /2 hours, 28 parts benzyl cyanide are then added, and boiling is continued for a further. 30 minutesJThe mixture is then cooled to 40. After filtering off with suction and washing with 50% ethanol, there are obtained 59.5 parts a-phenyl-B-(2N,N-dimethy1- sulphamidoxy-4-amino-phenyl)-acry1onitri1e of m.p. 153 to 154. 1

1f the benzyl cyanide is replaced-with corresponding amounts of the following substituted acetonitriles, then the substituted acrylonitriles mentioned below are obtained in similar yields: p-tolyl-acetonitrile yields a-(p-tolyl)-3-(2-N,N- dimethyl-sulphamidoxy-4-amino-phenyl)-acrylonitrile of m.p. 181 to 182; 4-methoxybenzyl-cyanide yields a-( 4-methoxy phenyl)- B-(2'N,N-dimethy1sulphamidoxy-4-amino-phenyl)- acrylonitrile of m.p. 169 to 171; 4-chlorobenzylcyanide yields oz-(4-chloropheny1)-B-( 2- N,N-dimethyl-sulphamidoxy-4-amino-phenyl)- acrylonitrile of 198 to 199; 3,4-dichlorobenzyl cyanide yields a-(3,4-dichlorophenyl)-B(2-N,N-dimethylsulphamidoxy-4-aminophenyl)-acrylonitrile of m.p. 195 to 196; naphthyl-l-acetonitrile yields a-(naphthyl-U-B-(Z- N,N-dimethyl-sulphamidoxy-4-aminophenyl)- acrylonitrileof m.p. 154 to 156; napthyl-2-acetonitrile yields a-(naphthyl-2)-B-(2N,N- dimethyl-sulphamidoxy-4-aminophenyl)-acrylonitrile of m.p. to 192; thienyl-Z-acetonitrile yields a-(thienyl-2)-B-(2-N,N- dimethyl-sulphamidoxy-4-aminophenyl)-acrylonitrile of m.p. 207 to 208; pyridine-2-acetonitrile yields a-(pyridyl-2)-B-(2N,N- dimethyl-sulphamidoxy-4-aminophenyl)-acrylonitrile of m.p. 168 to 169.

EXAMPLE 4 A solution of 72 parts N,N-dimethyl-sulphamic acid- (2-methyl-5-nitro-phenyl) ester in 158 parts ethanol and 100 parts of water is mixed at boiling temperature with a solution of 24 parts Na- S 9 H 0, 19 parts NaOH and 10 parts sulphur in 100 parts of water. The mixture is boiled for l /zhours, 26 parts cyanoacetic acid ethyl ester are added, and boiling is continued for 30 minutes. Aftercooling, the mixture is adjusted to pH to 6 with acetic. acid. After filtering off with suction, there are obtained 35 parts a-carbohydroxy-B-(2-N,N- dimethyl-sulphamidoxy-4-amino-phenyl)-acrylonitrile of m.p. 234 to 235 (decomp.). A

EXAMPLE 5 A solution of 2-N,N-dimethyl-sulphamidoxy-4- amino-benzaldehyde prepared as in Example 4 is admixed at boiling temperature with a solution of 38 parts benzimidazolyl-2-acetonitrile in 100 parts of a sodium hydroxide solution, the mixture is boiled for 1 hour, and CO is introduced at boiling temperature until the product is completely precipitated. After cooling and filtering off with suction, there are obtained 45 parts a-(benzimidazolyl-Z)-B-(2-N,Ndimethylsulphamidoxy-4-amino-phenyl)-acrylonitrile of m.p. 231 to 233.

EXAMPLE 6 A solution of 24 parts Na S 9 H 0, 27 parts NaOH and 10 parts sulphur in 100 parts of water is added dropwise to a boiling solution of 76 parts 2-N.,N- dimethyl-sulphamidoxy-4-nitro-l ,S-dimethyl-benzene in 158 parts ethanol and 100 parts of water. The mixture is boiled for 1% hours, 28 parts benzyl cyanide .are then added, and boiling is continued for one-half hour. After cooling to 30 and filtering off with suction, there are obtained 34.5 parts a-phenyl-B-(2-N,N-dimethylsulphamidoxy-4-amino-5-methyl-phenyl)-acrylonitrile of m.p. l43 to 144.

EXAMPLE 7 A solution of 24 parts Na s 9 H 0, 19 parts NaOH and 10 parts sulphur in 100 parts of water is poured within to minutes into a boiling solution of 70.5 parts of the sodium salt of sulphuric-acid-(Z-methyl-S- nitro-phenyl) semiester in 158 parts ethanol and 100 parts of water. The mixture is boiledfor 1% hours, 28 parts benzyl cyanide are added, andboiling is continued for another hour. After cooling, the .mixture is acidified with dilute sulphuric acid. The residue is dissolved in a 10% sodium carbonate solution, the solution is clarified with active charcoal and then reacidified with dilute sulphuric acid; There are thus obtained parts of a yellow, non-melting product which, according to spectral findings, has the structure of a-phenyl-B-(2-hydrogensulphato-4-amino-phenyl)- acrylonitrile.

We claim: v I. B-phenyl-acrylic acid nitrile or the formula a N 0R l0 2 I f in which X is H or alkyl or l-4 carbon atoms; n is a number of 0 to 3; R isphenyl; naphthyl; carboxylyor phenyl substituted with chloro, methyl, methoxy or methyl sulfonyl; I

2 R is -sou R and R are methyl .or ethyl; and

25 ZisH,NaorK..

2; The B phe nyl acr'ylic acid nitrile ofclaim'l in which 3. The B-phenyl-acrylic acid nitrile of claim 1 in which R is --SO -,Z.

4. B-phenyl-acrylic acid'nitrile of claim I having the RiS -s2-N 

1. B-PHENYL-ACRYLIC ACID NITRILE OR THE FORMULA
 2. The Beta -phenyl-acrylic acid nitrile of claim 1 in which
 3. The Beta -phenyl-acrylic acid nitrile of claim 1 in which R is -SO3Z.
 4. Beta -phenyl-acrylic acid nitrile of claim 1 having the formula 